High-strength hydraulic cement compositions

ABSTRACT

A high-strength hydraulic cement composition contains cement, fine aggregates, coarse aggregates, water and a specified admixture and has a unit amount of water in the range of 120-185 kg/m 3 . Water and the cement are contained at a ratio of 20-40% and the admixture is contained in the amount of 0.1-3.0 weight parts per 100 weight parts of the cement. The admixture is one or more selected from reaction mixtures obtained by specified two processes and partially or completely neutralized substances obtained from such a reaction mixture through these two processes and also a specified third process. The specified two processes include initiating a radical copolymerization process of a radical polymerizable monomer mixture containing maleic anhydride and a monomer of a specified kind in a non-aqueous system in the presence of a non-aqueous radical initiator and stopping the radical copolymerization reaction in its midst while the inversion rate of polymerization is at a specified level by adding water to the reaction system to thereby obtain a reaction mixture. The specified third process is for partially or completely neutralizing the reaction mixture.

Priority is claimed on Japanese Patent Application 2003-370285 filed Oct. 30, 2003.

BACKGROUND OF THE INVENTION

This invention relates to high-strength hydraulic cement compositions (say, for the production of high-strength hydraulic concrete) and more particularly to high-strength hydraulic cement compositions having simultaneously a plurality of specified characteristics that are desirable to such compositions.

High-strength hydraulic cement compositions are produced by kneading water and cement together at a smaller mixing ratio than for the production of normal-strength hydraulic cement compositions. Because of their very nature, these high-strength hydraulic cement compositions generally have several problems such that it takes a long time for the kneading, that the drop in fluidity with time (hereinafter referred to as the slump loss) is large, that the viscosity is too high, that the autogeneous shrinkage of the hardened object obtained from them is too large and that the strength of such a hardened object is not sufficiently high. In view of such problems, Japanese Patent Publication Tokkai 3-93660 and U.S. Pat. No. 6,642,320 disclosed the use of high-quality cement dispersants as admixtures and Japanese Patent Publications Tokkai 2001-220194, 2001-48620 and 2001-270759 disclosed the use of shrinkage reducing agents as admixtures, but these prior art high-strength hydraulic cement compositions cannot simultaneously solve all of the plurality of problems described above.

SUMMARY OF THE INVENTION

It is therefore an object of this invention to provide high-strength hydraulic cement compositions capable of simultaneously satisfying the plurality of conditions that the time required for the kneading should be short, that the slump loss should be small, that the viscosity should be small, that the autogeneous shrinkage of the hardened object obtained from them should be small and further that the strength of such a hardened object should be sufficiently high as desired.

The present invention is based on the discovery by the present inventors as a result of their diligent studies in view of the object described above that high-strength hydraulic cement compositions containing cement, fine aggregates, coarse aggregates, water and a specified admixture, having a specified water-to-cement ratio and a specified unit amount of water and further containing an admixture of a specified kind at a specified ratio with respect to the cement can satisfy these conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph obtained from a reaction mixture obtained as the admixture of this invention when it was analyzed by gel-permeation chromatography.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to high-strength hydraulic cement compositions characterized as comprising cement, fine aggregates, coarse aggregates, water and an admixture of a specified kind described below, containing the water and the cement at a ratio of 20-40%, having a unit amount of water in the range of 120-185 kg/m³ and containing the admixture in the amount of 0.1-3.0 weight parts per 100 weight parts of the cement. In the above, the admixture of the specified kind is one or more selected from reaction mixtures obtained by Process 1 and Process 2 and partially or completely neutralized substances obtained further by Process 3, where Process 1 is a process of initiating a radical copolymerization process of a radical polymerizable monomer mixture containing maleic anhydride and a monomer shown by Formula 1 by 97 molar % or more at a molar ratio of 50/50-70/30 in a non-aqueous system in the presence of a non-aqueous radical initiator, Process 2 is a process of stopping the radical copolymerization reaction initiated in Process 1 in the midst of the reaction when the inversion rate of polymerization defined by {(TM−UM)/TM}×100 has become 50-90% by adding water to the reaction system and thereby obtaining a reaction mixture containing a copolymer thus produced and residual monomers, TM indicating the total weight of the radical polymerizable monomer mixture at the start of the radical polymerization reaction in Process 1 and UM indicating the total weight of the residual monomers when the radical copolymerization reaction is stopped in Process 2, Process 3 is a process of partially or completely neutralizing the reaction mixture obtained in Process 2 by one or two selected from alkali metal hydroxides, alkali earth metal hydroxides and amines, and Formula 1 is given by CH₂═CH—CH₂—O—A—O—R where R is methyl group, acetyl group or hydrogen atom and A is a residual group obtained by removing all hydroxyl groups from (poly)alkyleneglycol having (poly)oxyalkylene groups formed with 1-150 oxyethylene units or a total of 2-150 oxyethylene and oxypropylene units.

High-strength hydraulic cement compositions according to this invention comprise cement, fine aggregates, coarse aggregates, water and an admixture, and examples of the admixture according to this invention include (1) reaction mixtures obtained by Processes 1 and 2, (2) partially or completely neutralized products of such a reaction mixture obtained further through Process 3, and one or more selected from (1) and (2). In other words, admixtures of this invention include one or more selected from the reaction mixtures of (1), one or more selected from the partially or completely neutralized products of (2) and the mixtures of the above.

Process 1 is a process of initiating a radical copolymerization process of a radical polymerizable monomer mixture in a non-aqueous system in the presence of a non-aqueous radical initiator. Examples of the radical polymerizable monomer mixture that may be used include those containing maleic anhydride and monomer shown by Formula 1 by 97 molar % or more as a total and preferably by 100 molar % at a molar ratio of 50/50-70/30 or preferably 55/45-65/35.

Regarding Formula 1, R may be methyl group, acetyl group or hydrogen atom but preferably be methyl group or acetyl group.

Regarding Formula 1, examples of what A may be include (1) residual groups obtained by removing all hydroxyl groups from (poly) ethyleneglycol having within its molecule (poly)oxyethylene groups entirely made of oxyethylene units and (2) residual groups obtained by removing all hydroxyl groups from (poly)ethylene(poly)propyleneglycol having within its molecules (poly)oxyethylene(poly)oxypropylene group made of both oxyethylene units and oxypropylene units, but examples of (1) are preferable. In the case of (2), the oxyethylene units and oxypropylene units may be in random or block combination but examples with random combination are preferable. The repetition number of the oxyalkylene units (such as oxyethylene) in A may be 1-150 and preferably 15-90.

In other words, preferable monomers are those shown by Formula 1 where R is methyl group or acetyl group and A is a residual group obtained by removing all hydroxyl groups from polyethyleneglycol having polyoxyethylene groups made of 15-90 oxyethylene units.

Examples of such monomers shown by Formula 1 as explained above include (1) α-allyl-ω-methoxy-(poly)oxyethylene; (2) α-allyl-ω-methoxy-(poly)oxyethylene (poly)oxypropylene; (3) α-allyl-ω-acetoxy-(poly)oxyethylene; (4) α-allyl-ω-acetoxy-(poly)oxyethylene (poly)oxypropylene; (5) α-allyl-ω-hydroxy-(poly)oxyethylene; and (6) α-allyl-ω-hydroxy-(poly)oxyethylene-(poly)oxypropylene.

The radical polymerizable monomer mixture to be used in Process 1 is a mixture containing maleic anhydride and monomer shown by Formula 1 by 97 molar % or more as a total and preferably by 100 molar %. This means that radical polymerizable monomers of other types may be contained by 3 molar % or less. Examples of such radical polymerizable monomers of other types include styrene, vinyl acetate, acrylic acid, salts of acrylic acid, alkyl acrylates, (metha)allyl sulfonic acid and salts of (metha)allyl sulfonic acid.

Process 1 is a process of initiating a radical copolymerization process in a non-aqueous system by adding a non-aqueous radical initiator to a radical polymerizable monomer mixture as explained above. Methods of initiating a radical copolymerization process in a non-aqueous system include (1) methods of initiating a radical copolymerization process without using any solvent, and (2) methods of initiating a radical copolymerization process by using a non-aqueous solvent such as benzene, toluene, xylene, methyl isobutylketone and dioxane and dissolving the radical polymerizable monomer mixture in such a non-aqueous solvent, but the methods of (1) are preferable. A radical copolymerization reaction according to a method of (1) may be initiated, for example, by setting the radical polymerizable monomer mixture in a reactor, adding a non-aqueous radial initiator to it in a nitrogen atmosphere and heating it to 40-60° C. Examples of the non-aqueous radical initiator that may be used in Process 1 include azo initiators such as azobisisobutyronitrile and 2,2′-azobis(4-methoxy 2,4-dimethyl valeronitrile), benzoyl peroxide, lauroyl peroxide and kumene hydroperoxide.

Process 2 is a process of stopping the radical copolymerization reaction initiated in Process 1 in the midst of the reaction while the inversion rate of polymerization defined above becomes 50-90% by adding water to the reaction system and thereby obtaining a reaction mixture containing a copolymer thus produced and residual monomers. In Process 2, the radical copolymerization reaction initiated in Process 1 is stopped during the reaction while the inversion rate of polymerization defined above becomes 50-90%, or preferably 65-85%. Methods of stopping the radical copolymerization reaction in the midst of the reaction while the inversion rate of polymerization becomes 50-90%, or preferably 65-85%, include (1) method of sampling a portion of the reaction mixture from the reaction system periodically, obtaining the ratio of the generated copolymer and the residual monomers by a high-speed method of analysis such as GPC or high-speed liquid chromatography, calculating the inversion rate of polymerization by using the obtained number and thereby determining the time to stop the radical copolymerization reaction; (2) method of preliminarily obtaining the relationship between the torque of the stirrer used for the reaction system and the inversion rate of polymerization and stopping the radical copolymerization reaction on the basis of the obtained relationship at the time when the torque reaches the value corresponding to the desired inversion rate of polymerization; and (3) method of preliminarily obtaining the relationship between the time of the radical copolymerization reaction and the inversion rate of polymerization and stopping the radical copolymerization based on the obtained relationship at the time corresponding to the desired inversion rate of polymerization. From the point of view of freedom and simplicity of equipment, however, the method of (3) is preferable. In any case, if the radical copolymerization reaction is stopped in the midst when the inversion rate of polymerization is not within the range of 50-90%, high-strength hydraulic cement compositions simultaneously possessing the desired plurality of functions cannot be obtained by using such an admixture.

The invention does not impose any stringent restriction regarding the temperature at the start of the radical copolymerization reaction of Process 1 or during Process 2 while the radical copolymerization reaction is continued until it is stopped in the midst but it is preferably in the range of 60-90° C. Neither is there any restriction imposed on the amount of water to be added for stopping the radical copolymerization reaction in Process 2 but it is preferably 2-10 mols per mol of the maleic anhydride used as the material.

Thus, a reaction mixture containing the generated copolymers and residual monomers is obtained by Process 2. From the point of view of the radical polymerizable monomer mixture used for the radical copolymerization reaction of Process 1, the copolymers that are generated and come to be contained in the reaction mixture are those with constituent units formed with maleic anhydride and monomers shown by Formula 1 but since this radical copolymerization reaction is stopped in the midst of Process 1 by adding water, the constituent units formed with maleic anhydride become constituent units formed with maleic acid as a result of hydrolysis of maleic anhydride. Similarly, from the point of view of the radical polymerizable monomer mixture used for the radical copolymerization reaction of Process 1, the residual monomers that come to be contained in the reaction mixture are those containing at least maleic anhydride and/or monomers shown by Formula 1, but since this radical copolymerization reaction is stopped in the midst of Process 1 by adding water, maleic anhydride becomes maleic acid as a result of hydrolysis.

There is no limitation imposed on the molecular weight of the copolymers that come to be contained in the reaction mixture in Process 2, but those with the top of peak of weight-average molecular weight (hereinafter pullulan converted weight in the measurement by gel-permeation chromatography (or GPC) of 30000-45000 are preferred. Adjustment of weight-average molecular weight can be accomplished by appropriately selecting the kind and the amount of the non-aqueous radical initiator used in Process 1, the kind and amount of the radical chain transfer agent which may be added if necessary in Processes 1 and 2 and the temperature and time of the radical copolymerization in Processes 1 and 2.

Process 3 is a process of partially or completely neutralizing the reaction mixture obtained in Process 2 by means of a basic compound to obtain partially or completely neutralized objects of the aforementioned reaction mixture. Examples of the basic compound to be used for this purpose include (1) alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; (2) alkali earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and (3) amines such as ammonia and triethanol amine, but alkali metal hydroxides are preferred.

High-strength hydraulic cement compositions according to this invention comprise cement, fine aggregates, coarse aggregates, water and an admixture as described above. Examples of cement that may be used include (1) portland cement of different kinds such as normal portland cement, high early strength portland cement, moderate heat portland cement and low heat portland cement, (2) mixed cement of different kinds such as blast-furnace slag cement, fly ash cement and silica fume cement, and (3) alumina cement. Different kinds of portland cement with a portion replaced with a microscopic powder admixture such as blast-furnace slag microscopic powder, silica fume microscopic powder and fly ash microscopic powder may be used as cement in a broader sense of the word. High-strength hydraulic cement compositions of this invention are particularly effective when moderate heat portland cement is used as the cement material. Examples of fine aggregates include river sand, mountain sand, ocean sand and crushed sand. Examples of coarse aggregates include river stones, crushed stones and light-weight aggregates.

The water-to-cement ratio for high-strength hydraulic cement compositions of this invention is 20-40% but it is preferable to keep it within the range of 25-35%. The unit amount of water is within the range of 120-185 kg/m³ but it is preferable to keep it within the range of 140-175 kg/m³. The amount of the admixture to be used is 0.1-3.0 weight parts per 100 weight parts of the cement but it is preferable to keep it within the range of 0.15-1.0 weight parts. High-strength hydraulic cement compositions of this invention within such limitations can simultaneously possess the plurality of originally desired characteristics.

Other kinds of additives such as an air content controlling agent, a hardening accelerator, a hardening retarder, a drying shrinkage reducing agent, a water-proofing agent, a preservative and an anti-rust agent may be added to the high-strength hydraulic cement compositions of this invention within the limit of not adversely affecting the effects of the present invention.

High-strength hydraulic cement compositions of this invention can simultaneously satisfy many conditions such that the time required for kneading should be short, that the slump loss should be small, that the viscosity should be small, that hardened objects obtained therefrom should have a small autogeneous shrinkage and that hardened objects obtained therefrom should have a desired high strength.

The invention is described next in terms of the following sixteen embodiments.

(1) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-1) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.25 weight parts of Admixture (A-1) being contained per 100 weight parts of the cement, wherein Admixture (A-1) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-polyoxyethylene (molar number of oxyethylene units (=n) being 33) at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 83% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 38000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=33)oxyethylene.

(2) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-2) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.3 weight parts of Admixture (A-2) being contained per 100 weight parts of the cement, wherein Admixture (A-2) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methyl-poly(n=68)oxyethylene at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 78% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 40300 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=68)oxyethylene.

(3) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-3) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.24 weight parts of Admixture (A-3) being contained per 100 weight parts of the cement, wherein Admixture (A-3) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=23)oxyethylene at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 77% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 35700 and residual monomers of maleic acid and α-allyl-ω-methyoxy-poly(n=23)oxyethylene.

(4) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-4) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.26 weight parts of Admixture (A-4) being contained per 100 weight parts of the cement, wherein Admixture (A-4) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=50)oxyethylene at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 80% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 39000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=50)oxyethylene.

(5) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-6) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.34 weight parts of Admixture (A-6) being contained per 100 weight parts of the cement, wherein Admixture (A-6) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=80)oxyethylene-polyoxypropylene (molar number of oxypropylene units (=m) being 5) at molar ratio of 55/45 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 68% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 34000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=80)oxyethylene-poly(m=5)oxypropylene.

(6) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-7) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.24 weight parts of Admixture (A-7) being contained per 100 weight parts of the cement, wherein Admixture (A-7) is a reaction mixture obtained by Process 1 and Process 2 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=80)oxyethylene-poly(m=5)oxypropylene at molar ratio of 65/35 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 75% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 37000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=80)oxyethylene-poly(m=5)oxypropylene.

(7) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-8) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.26 weight parts of Admixture (A-8) being contained per 100 weight parts of the cement, wherein Admixture (A-8) is a partially neutralized object obtained by Process 1, Process 2 and Process 3 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=33)oxyethylene at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 83% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 38000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=33)oxyethylene.

Process 3: Process of partially neutralizing the reaction mixture obtained in Process 2 with sodium hydroxide and thereby obtaining partially neutralized object of this reaction mixture.

(8) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and Admixture (A-9) described below with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.27 weight parts of Admixture (A-9) being contained per 100 weight parts of the cement, wherein Admixture (A-9) is a completely neutralized object obtained by Process 1, Process 2 and Process 3 described below:

Process 1: Process of initiating a radical copolymerization reaction of a radical polymerizable monomer mixture containing maleic anhydride and α-allyl-ω-methoxy-poly(n=50)oxyethylene at molar ratio of 60/40 in a non-aqueous system without using any solvent and in the presence of azobisisobutyronitrile.

Process 2: Process of stopping the radical copolymerization reaction initiated in Process 1 in its midst by adding water to its reaction system when the inversion rate of polymerization defined above becomes 80% and thereby obtaining reaction mixture containing produced copolymers with weight-average molecular weight of 39000 and residual monomers of maleic acid and α-allyl-ω-methoxy-poly(n=50)oxyethylene.

Process 3: Process of completely neutralizing the reaction mixture obtained in Process 2 with sodium hydroxide and thereby obtaining completely neutralized object of this reaction mixture.

(9) High-strength hydraulic cement composition containing normal portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-1) with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.29 weight parts of Admixture (A-1) being contained per 100 weight parts of the cement.

(10) High-strength hydraulic cement composition containing normal portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-3) with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.28 weight parts of Admixture (A-3) being contained per 100 weight parts of the cement.

(11) High-strength hydraulic cement composition containing normal portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-6) with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.40 weight parts of Admixture (A-6) being contained per 100 weight parts of the cement.

(12) High-strength hydraulic cement composition containing normal portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-7) with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.27 weight parts of Admixture (A-7) being contained per 100 weight parts of the cement.

(13) High-strength hydraulic cement composition containing normal portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-8) with the water-to-cement ratio of 30% and unit amount of water 170 kg/m³, 0.30 weight parts of Admixture (A-8) being contained per 100 weight parts of the cement.

(14) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-1) with the water-to-cement ratio of 25% and unit amount of water 160 kg/m³, 0.42 weight parts of Admixture (A-1) being contained per 100 weight parts of the cement.

(15) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-3) with the water-to-cement ratio of 25% and unit amount of water 160 kg/m³, 0.40 weight parts of Admixture (A-3) being contained per 100 weight parts of the cement.

(16) High-strength hydraulic cement composition containing moderate heat portland cement, fine aggregates, coarse aggregates, water and aforementioned Admixture (A-8) with the water-to-cement ratio of 25% and unit amount of water 160 kg/m³, 0.44 weight parts of Admixture (A-8) being contained per 100 weight parts of the cement.

TEST EXAMPLES

In what follows, some test examples are shown in order to further explain the invention and its effects but these examples are not intended to limit the scope of the invention.

Part 1 (Synthesis of Admixtures)

Synthesis of Admixture (A-1)

Maleic anhydride 147 g (1.5 moles) and α-allyl-ω-methoxy-poly(n=33)oxyethylene 1524 g (1.0 mole) were placed inside a reactor and after they were dissolved uniformly with stirring, the atmosphere was replaced with nitrogen. While the reacting system was maintained at 80° C. with a hot water bath, azobisisobutylonitrile 5.8 g was added to start a radical polymerization reaction. After 2 hours of the radical copolymerization process, it was stopped by adding 80 g of water to the reacting system to obtain a reaction mixture. This reaction mixture was analyzed by GPC and found as a result to contain copolymer with weight-average molecular weight of 38000 with a constituent unit formed with maleic acid and a constituent unit with α-allyl-ω-methoxy-poly(n=33)oxyethylene, maleic acid and α-allyl-ω-methoxy-poly(n=33)oxyethylene, and its inversion ratio of polymerization defined above was 83%. This reaction mixture is referred to as Admixture (A-1).

FIG. 1 shows the GPC graph of the reaction mixture of Admixture (A-1). In FIG. 1, numeral 1 indicates the peak of the generated copolymer, numeral 2 indicates the peak of α-allyl-ω-methoxy-poly(n=33)oxyethylene, numeral 3 indicates the peak of maleic acid and numeral 4 shows the peak top.

Syntheses of Admixtures (A-2)-(A-7)

Admixtures (A-2)-(A-7) were synthesized similarly as explained above.

Synthesis of Admixture (A-8)

A 40% aqueous solution 500 g of aforementioned Admixture (A-1) was placed inside a reactor and a 30% aqueous solution of sodium hydroxide 29 g was gradually added with stirring to carry out partial neutralization and to thereby obtain partially neutralized object of reaction mixture with degree of neutralization 60%. This is referred to as Admixture (A-8).

Synthesis of Admixture (A-9)

A 40% aqueous solution 500 g of aforementioned Admixture (A-4) was placed inside a reactor and a 30% aqueous solution of sodium hydroxide 32.7 g was gradually added with stirring to carry out complete neutralization and to thereby obtain completely neutralized object of reaction mixture with degree of neutralization 100%. This is referred to as Admixture (A-9).

Synthesis of Admixture (R-1)

Maleic anhydride 147 g (1.5 moles) and α-allyl-ω-methoxy-poly(n=33)oxyethylene 1524 g (1.0 mole) were placed inside a reactor and after they were dissolved uniformly with stirring, the atmosphere was replaced with nitrogen. While the reacting system was maintained at 80° C. with a hot water bath, azobisisobutylonitrile 5.8 g was added to start a radical polymerization reaction. After 50 minutes of the radical copolymerization process, it was stopped by adding 80 g of water to the reacting system to obtain a reaction mixture. This reaction mixture is referred to as Admixture (R-1).

Syntheses of Admixtures (R-2)-(R-7)

Admixtures (R-2)-(R-7) were synthesized similarly as explained above re Admixture (R-1).

Synthesis of Admixture (R-8)

As done for Admixture (A-9), Admixture (R-2) was completely neutralized with sodium hydroxide to obtain completely neutralized object. This is referred to as Admixture (R-8).

Details of these Admixtures obtained as above are summarized in Table 1.

TABLE 1 Process 1 Monomers (molar %) Process 2 Process 3 (X) Maleic (Y) Monomers (X)/(Y) Weight-average Basic Kind of anhydride of Formula 1 Molar IRP molecular weight compound Admixtures (molar %) (Kind/molar %). ratio (%) of copolymer used Text Example A-1 60 d-1/40 60/40 83 38000 A-2 60 d-2/40 60/40 78 40300 A-3 60 d-3/40 60/40 77 35700 A-4 60 d-4/40 60/40 80 39000 A-5 57 d-5/40 57/43 70 40800 d-6/3 A-6 55 d-5/45 55/45 68 34000 A-7 65 d-5/35 65/35 75 37000 A-8 60 d-1/40 60/40 83 38000 NaOH A-9 60 d-4/40 60/40 80 39000 NaOH Comparison Example R-1 60 d-1/40 60/40 43 29500 R-2 60 d-1/40 60/40 92 50000 R-3 60 d-4/40 60/40 93 53500 R-4 60 d-5/40 60/40 95 57500 R-5 60 dr-1/40 60/40 94 66700 R-6 45 d-5/55 45/55 69 35000 R-7 75 d-5/25 75/25 76 39000 R-8 60 d-1/40 60/40 92 50000 NaOH In Table 1: IRP: Inversion rate of polymerization d-1: α-allyl-ω-methoxy-poly(n = 33)oxyethylene d-2: α-allyl-ω-methoxy-poly(n = 68)oxyethylene d-3: α-allyl-ω-acetoxy-poly(n = 23)oxyethylene d-4: α-allyl-ω-acetoxy-poly(n = 50)oxyethylene d-5: α-allyl-ω-hydroxy-poly(n = 80)oxyethylene-poly(m = 5)oxypropylene d-6: Styrene dr-1: α-allyl-ω-acetoxy-poly(n = 170)oxyethylene Part 2 (Preparation and Evaluation of High-Strength Hydraulic Cement Compositions)

Test Examples 1-19 and Comparison Examples 1-27 (Preparation of High-Strength Hydraulic Cement Compositions)

Mixtures were kneaded together under the conditions shown in Table 2. For Mixtures No. 1 and No. 3, moderate heat portland cement (specific weight=3.22, blaine value =3390), fine aggregates (Ooi-gawa River sand with specific weight=2.58) and coarse aggregates (crushed stones from Okazaki with specific weight=2.68) were sequentially added into a forced-mixing pan-type mixer with capacity 50 liters and subjected to a free kneading process for 15 seconds. Next, the admixtures prepared in Part 1 and described in Table 1 were each kneaded together, added with water and kneaded for 240 seconds such that the target slump flow would be within the range of 60±5 cm and the target air content would be within the range of 3±0.5%. For Mixture No. 2, kneading was carried out similarly except that use was made of normal portland cement (specific weight=3.20, blaine value=3300).

TABLE 2 Unit amount (kg/m³) Moderate Fine Normal heat Water/cement aggregates portland portland Fine Coarse Mixture ratio (%) (%) Water cement cement aggregates aggregates No. 1 30 45.0 170 — 566 725 920 No. 2 30 45.0 170 566 — 721 915 No. 3 25 42.0 160 — 640 662 950 Evaluation of High-Strength Hydraulic Cement Compositions

For each of the high-strength hydraulic cement compositions thus prepared, the time for kneading, the slump flow, the air content and the L-flow velocity immediately after the kneading, as well as the slump flow and the air content 90 minutes after the kneading, the autogeneous shrinkage strain and the compressive strength were obtained as below. The results are shown together in Tables 3-8.

Slump flow: Measured according to JIS-A1150 on high-strength hydraulic cement compositions immediately after kneading and after 90 minutes of kneading and being left quietly on a boat.

Air content: Measured according to JIS-A1128 on high-strength hydraulic cement compositions immediately after kneading and after 90 minutes of kneading and being left quietly on a boat.

Kneading time: A clamp meter (an electric current meter) was connected to the forced-mixing pan-type mixer to record the time of kneading and the waveform of the load current of the mixer by means of a recorder and the time required for the load current to reach the maximum value was recorded as the kneading time.

L-flow velocity: Measured by using an L-flow meter (described in “Recommendations for Mix Design and Construction Practice of High Fluidity Concrete” by Architectural Institute of Japan). The flow speed between 5 cm and 10 cm from the flow-starting surface of the L-flow meter was defined as the flow speed. If the slump flow is the same, a large initial L-flow speed corresponds to a low viscosity.

Autogeneous shrinkage strain: Measured at material ages of 1 day and 28 days according to the description in “Test Method for Autogeneous Shrinkage and Autogeneous Expansion of Concrete” by Autogeneous Shrinkage Research Committee of the Japan Concrete Institute. A smaller numerical value of autogeneous shrinkage strain indicates a smaller antogeneous shrinkage. Since the autogeneous shrinkage strain tends to become large for high-strength hydraulic cement compositions with a small water-to-cement ratio, it is necessary to compare the autogeneous shrinkage strain values among high-strength hydraulic cement compositions with the same water-to-cement ratio.

Compressive strength: Measured at material ages of 7 days and 28 days according to JIS-A1108.

TABLE 3 Immediately after kneading After 90 minutes Mixture Admixture L-flow Slump Air Slump Air No. in Kind/ Kneading velocity flow content flow content Table 2 Amount time (sec) (cm/s) (cm) (%) (cm) (%) Test Examples 1 1 A-1/0.25 47 12.5 60.5 3.1 56.2 2.9 2 1 A-2/0.30 58 12.2 61.2 3.3 55.7 3.0 3 1 A-3/0.24 45 13.0 60.5 3.0 55.4 2.8 4 1 A-4/0.26 49 12.4 60.7 3.2 56.0 3.1 5 1 A-5/0.33 63 12.0 61.5 3.1 56.3 3.0 6 1 A-6/0.34 69 12.1 60.2 3.0 56.5 3.1 7 1 A-7/0.24 45 11.4 60.2 2.9 53.6 2.9 8 1 A-8/0.26 45 12.7 61.0 3.3 54.4 3.0 9 1 A-9/0.27 47 12.5 61.1 3.0 54.0 2.8 Comparison Examples 1 1 R-1/*3 — — — — — — 2 1 R-2/0.27 94 9.3 61.0 3.0 42.6 2.8 3 1 R-3/0.29 98 9.0 60.7 2.8 42.6 2.9 4 1 R-4/0.45 95 8.8 60.5 3.2 44.5 3.1 5 1 R-5/0.59 120 7.9 60.2 3.1 43.8 3.0 6 1 R-6/0.52 110 9.0 60.0 3.2 45.2 3.0 7 1 R-7/0.26 88 8.2 61.8 3.2 41.3 3.1 8 1 R-8/0.28 90 9.5 61.3 3.3 42.0 3.0 9 1 R-9/0.40 105 8.5 60.7 2.9 43.5 3.0 10  1 R-10/0.34 110 8.4 60.4 3.0 43.2 3.1 11  1 R-11/0.42 107 8.2 60.8 3.2 41.7 3.0 12  1 R-12/0.30 93 8.7 60.3 3.3 44.6 3.1 In Table 3: Amount of admixture”: Added weight part as solid component of admixture per 100 weight parts of cement; *3: Target flow value was not obtained for lack of fluidity although the added amount was increased; R-9: Mixture of Admixture (R-2) and monomer (d-1) at solid component weight ratio of 80/20; R-10: Mixture of Admixture (R-2) and maleic acid at solid component weight ratio of 97.5/2.5; R-11: Mixture of Admixture (R-2), monomer (d-1) and maleic acid at solid component weight ratio of 80/17.5/2.5; R-12: High-range water reducing agent for high-strength hydraulic cement compositions (tradename: Chupol HP-11, produced by Takemoto Yushi Kabushiki Kaisha).

TABLE 4 Immediately after kneading After 90 minutes Mixture Admixture L-flow Slump Air Slump Air No. in Kind/ Kneading velocity flow content flow content Table 2 Amount time (sec) (cm/s) (cm) (%) (cm) (%) Test Examples 10 2 A-1/0.29 49 11.3 60.6 3.1 55.2 3.0 11 2 A-3/0.28 46 11.9 60.3 3.0 54.8 2.8 12 2 A-5/0.39 65 11.2 61.4 3.3 54.2 3.0 13 2 A-6/0.40 70 11.5 60.8 3.1 55.1 3.0 14 2 A-7/0.27 48 11.1 60.0 3.0 53.0 2.9 15 2 A-8/0.30 48 12.0 61.2 3.2 54.3 3.0 Comparison Examples 13 2 R-1/*3 — — — — — — 14 2 R-2/0.30 96 9.0 60.8 3.3 43.8 2.8 15 2 R-3/0.34 102 8.8 60.5 3.3 45.1 3.0 16 2 R-4/0.57 99 8.5 61.2 2.9 46.3 2.7 17 2 R-5/0.69 135 7.3 61.0 3.2 45.6 2.9 18 2 R-6/0.65 115 8.9 61.0 3.0 46.6 2.8 19 2 R-7/0.29 92 8.0 60.2 2.9 43.2 3.0 20 2 R-8/0.31 93 9.1 61.1 2.9 44.0 3.1

TABLE 5 Immediately after kneading After 90 minutes Mixture Admixture L-flow Slump Air Slump Air No. in Kind/ Kneading velocity flow content flow content Table 2 Amount time (sec) (cm/s) (cm) (%) (cm) (%) Test Examples 16 3 A-1/0.42 70 9.7 61.6 2.9 57.8 2.9 17 3 A-3/0.40 68 9.9 62.0 2.8 58.2 2.9 18 3 A-5/0.53 77 9.5 61.5 3.0 56.7 3.1 19 3 A-8/0.44 73 10.0 61.3 2.9 58.1 3.0 Comparison Examples 21 3 R-1/*3 — — — — — — 22 3 R-2/0.47 105 6.8 61.3 3.0 46.8 2.7 23 3 R-3/0.58 127 6.0 61.0 2.8 41.5 3.0 24 3 R-4/0.67 138 5.4 61.4 2.9 40.2 3.2 25 3 R-5/*3 — — — — — — 26 3 R-7/*3 — — — — — — 27 3 R-8/0.46 101 6.2 61.4 2.8 40.0 2.8

TABLE 6 Autogeneous shrinkage Compressive strength strain (×10⁻⁴) (N/mm²) Age 1 day Age 28 days Age 7 days Age 28 days Test Examples 1 1.5 2.7 67 84 2 1.6 2.8 65 82 3 1.4 2.6 67 84 4 1.5 2.7 65 81 5 1.6 2.7 67 83 6 1.4 2.6 65 80 7 1.6 2.8 79 100  8 1.5 2.7 68 84 9 1.6 2.7 68 84 Comparison Examples 1 — — — — 2 2.0 3.3 62 77 3 1.9 3.2 60 75 4 2.0 3.3 63 78 5 2.0 3.3 59 73 6 2.0 3.3 63 77 7 1.9 3.3 61 73 8 1.9 3.2 59 73 9 1.8 3.1 59 73 10  2.0 3.4 62 75 11  1.9 3.3 61 74 12  2.0 3.4 67 80

TABLE 7 Autogeneous shrinkage Compressive strength strain (×10⁻⁴) (N/mm²) Age 1 day Age 28 days Age 7 days Age 28 days Test Examples 10 1.6 2.8 79 98 11 1.6 2.9 77 96 12 1.7 2.8 79 98 13 1.5 2.7 74 95 14 1.6 2.8 79 100  15 1.7 2.8 80 99 Comparison Examples 13 — — — — 14 2.0 3.5 70 92 15 2.1 3.6 67 90 16 2.1 3.6 69 93 17 2.0 3.5 66 89 18 2.0 3.5 67 89 19 2.1 3.6 70 91 20 2.1 3.5 68 91

TABLE 8 Autogeneous shrinkage Compressive strength strain (×10⁻⁴) (N/mm²) Age 1 day Age 28 days Age 7 days Age 28 days Test Examples 16 2.5 4.6 74 103 17 2.6 4.7 74 107 18 2.4 4.5 75 105 19 2.3 4.4 73 101 Comparison Examples 21 — — — — 22 3.4 5.8 67  96 23 3.4 5.8 66  94 24 3.3 5.7 65  94 25 — — — — 26 — — — — 27 3.5 5.8 68  94 

1. A high-strength hydraulic cement composition comprising cement, fine aggregates, coarse aggregates, water and an admixture, said hydraulic cement composition containing water and said cement at a weight ratio of 20-40%, having a unit amount of water 120-185 kg/m³ and containing 0.1-3.0 weight parts of said admixture per 100 weight parts of said cement, said admixture comprising one or more selected from the group consisting of reaction mixtures obtained by Process 1 and Process 2 and partially or completely neutralized substances of said reaction mixtures obtained by said Process 1, said Process 2 and also Process 3 wherein said Process 1 is a process of initiating a radical copolymerization process of a radical polymerizable monomer mixture containing maleic anhydride and a monomer shown by Formula 1 by 97 molar % or more at a molar ratio of 50/50-70/30 in a non-aqueous system in the presence of a non-aqueous radical initiator, said Process 2 is a process of stopping the radical copolymerization reaction initiated in said Process 1 in the midst of the reaction when the inversion rate of polymerization defined by {(TM−UM)/TM}×100 has become 50-90% by adding water to the reaction system and thereby obtaining a reaction mixture containing a copolymer thus produced and residual monomers, TM indicating the total weight of the radical polymerizable monomer mixture at the start of the radical polymerization reaction in said Process 1 and UM indicating the total weight of the residual monomers when the radical copolymerization reaction is stopped in said Process 2, said Process 3 is a process of partially or completely neutralizing the reaction mixture obtained in said Process 2 by one or two selected from the group consisting of alkali metal hydroxides, alkali earth metal hydroxides and amines, and said Formula 1 is given by CH₂═CH—CH₂—O—A—O—R where R is methyl group, acetyl group or hydrogen atom and A is a residual group obtained by removing all hydroxyl groups from (poly)alkyleneglycol having (poly)oxyalkylene groups formed with 1-150 oxyethylene units or a total of 2-150 oxyethylene and oxypropylene units.
 2. The high-strength hydraulic cement composition of claim 1 wherein said Process 1 is a process of initiating a radical copolymerization process of a radical polymerizable monomer mixture without using any solvent in a non-aqueous system.
 3. The high-strength hydraulic cement composition of claim 1 wherein said reaction mixture of said Process 2 is obtained by stopping said radical copolymerization reaction in the midst of the reaction while the inversion rate of polymerization is 65-85%.
 4. The high-strength hydraulic cement composition of claim 2 wherein said reaction mixture of said Process 2 is obtained by stopping said radical copolymerization reaction in the midst of the reaction while the inversion rate of polymerization is 65-85%.
 5. The high-strength hydraulic cement composition of claim 1 wherein said Process 2 produces as reaction product copolymers with the top of peak of pullulan converted weight-average molecular weight of 30000-45000 in a measurement by gel-permeation chromatography.
 6. The high-strength hydraulic cement composition of claim 4 wherein said Process 2 produces as reaction product copolymers with the top of peak of pullulan converted weight-average molecular weight of 30000-45000 in a measurement by gel-permeation chromatography.
 7. The high-strength hydraulic cement composition of claim 1 wherein R is methyl group or acetyl group and A is residual group obtained by removing all hydroxyl groups from polyethyleneglycol having polyoxyethylene group with 15-90 oxyethylene units in said Formula
 1. 8. The high-strength hydraulic cement composition of claim 6 wherein R is methyl group or acetyl group and A is residual group obtained by removing all hydroxyl groups from polyethyleneglycol having polyoxyethylene group with 15-90 oxyethylene units in said Formula
 1. 9. The high-strength hydraulic cement composition of claim 1 wherein said cement is moderate heat portland cement.
 10. The high-strength hydraulic cement composition of claim 8 wherein said cement is moderate heat portland cement.
 11. The high-strength hydraulic cement composition of claim 1 containing water and said cement at a weight ratio of 25-35%.
 12. The high-strength hydraulic cement composition of claim 10 containing water and said cement at a weight ratio of 25-35%. 